ADVANCED BARRIER NICKEL OXIDE (BNiO) COATING DEVELOPMENT FOR THE PROCESS CHAMBER COMPONENTS

ABSTRACT

Described herein is a chamber component including a metal layer comprising nickel and a barrier layer of nickel oxide over the metal layer. The barrier layer of nickel oxide may be formed by treating the chamber component with an oxidizing agent comprising hydrofluoric acid and/or nitric acid

TECHNICAL FIELD

Embodiments of the present disclosure relate, in general, to erosionresistant metal oxide coated chamber components and methods of formingand using such coated chamber components.

BACKGROUND

In the semiconductor industry, devices are fabricated by a number ofmanufacturing processes producing structures of an ever-decreasing size.As device geometries shrink, controlling the process uniformity andrepeatability of devices becomes much more challenging.

Various semiconductor manufacturing processes use high temperatures,high energy plasma (such as remote and direct fluorine plasma such asNF₃, CF₄, and the like), a mixture of corrosive gases, corrosivecleaning chemistries (e.g., hydrofluoric acid) and combinations thereof.These extreme conditions may result in a reaction between materials ofcomponents within the process chamber and the plasma or corrosive gasesto form metal fluorides, particles, other trace metal contaminates andhigh vapor pressure gases (e.g., AlF_(x)). Such gases may readilysublime and deposit on other components within the chamber. During asubsequent process step, the deposited material may release from theother components as particles and fall onto the wafer causing defects.Additional issues caused by such reactions include deposition ratedrift, etch rate drift, compromised film uniformity, and compromisedetch uniformity. It is beneficial to reduce these defects with a stable,non-reactive coating on chamber components to limit the sublimationand/or formation of particles and metal contaminants on the chambercomponents within the chamber.

Hence, certain semiconductor processing chamber components (e.g.,liners, doors, lids, shower heads and so on) include an electrolessnickel plated (ENP) surface to reduce these defects. However, the ENPsurface has been found to develop a fluorine-containing layer after usein a fluorine-based atmosphere and at higher temperatures of about 150°C. or above. Without being limited to a theory, the fluorine-containinglayer develops because of contamination during use, thus thefluorine-containing layer can be considered a contamination layer.Further, after processing a few hundreds of wafers, it has been foundthat the fluorine-containing layer lessens the lifetime of one or morecomponents of the process chamber and a mean wafers between cleaning(MWBC) metric.

SUMMARY

In some embodiments of the present disclosure, a chamber component for aprocessing chamber may include a body; a metal plating on at least onesurface of the body, the metal plating comprising nickel; and a barrierlayer on the metal plating. In some embodiments, the barrier layer mayinclude a nickel oxide. In some embodiments, the metal plating mayinclude nickel and phosphorus. In some embodiments, the metal platingmay include nickel and is free of phosphorous. In some embodiments, thebody includes aluminum, an aluminum alloy, aluminum nitride, alumina, orcombinations thereof. In some embodiments, the metal plating has athickness of about 20 microns to about 75 microns, and the barrier layerhas a thickness of about 2 nm to about 50 nm. In some embodiments, thebarrier layer has an average surface roughness (Ra) of about 2micro-inches to about 60 micro-inches. In some embodiments, the chambercomponent may be a showerhead for a process chamber.

In other embodiments of the present disclosure, a method of protecting achamber component includes forming a metal plating on a body of thechamber component, wherein the metal plating may include nickel, andcontacting the metal plating with an oxidizing agent to form a barrierlayer on the metal plating, wherein the barrier layer may include nickeloxide. In some embodiments, the oxidizing agent may include one of atleast one of hydrofluoric acid, oxalic acid, or nitric acid. In someembodiments, the barrier layer may have a thickness from about 2 μm toabout 60 μm. In some embodiments, forming the metal plating may includeperforming electroless metal plating, and wherein the metal platingfurther comprises phosphorus. In some embodiments, the body may includean aluminum alloy, aluminum nitride, alumina, or combinations thereof.In some embodiments, the method may include removing a native oxide fromthe metal plating prior to forming the barrier layer. In someembodiments, the method may include after the forming the metal playing,forming a nickel fluoride (NiF2) or nickel oxy-fluoride layer on themetal plating by contacting the metal plating with ammonium fluoride. Insome embodiments, the method may also include placing the chambercomponent in an acid bath comprising 5-25% hydrofluoric acid and 75-95%water to contact the metal plating with the oxidizing agent;subsequently placing the chamber component in a de-ionized water bath;subsequently placing the chamber component in the acid bath; andsubsequently placing the chamber in the di-ionized water bath.

In another embodiment of the present disclosure, a method ofrefurbishing a used chamber component may include removing acontamination layer from a metal plating on the used chamber componentusing a first acid solution, wherein the metal plating comprises nickel;and subsequently contacting the metal plating with an oxidizing agent toform a barrier layer on the metal plating, wherein the barrier layercomprises nickel oxide. In some embodiments, the contamination layer mayinclude nickel fluoride. In some embodiments, the removing thecontamination layer may include placing the used chamber component in afirst acid bath, subsequently rinsing the used chamber component withdeionized water, subsequently drying the used chamber component,subsequently placing the used chamber component in a second acid bath,subsequently rinsing the used chamber component with deionized water,and subsequently drying the used chamber component. In some embodiments,the oxidizing agent may include at least one of hydrofluoric acid ornitric acid. In some embodiments, the barrier layer may have a thicknessfrom about 2 μm to about 60 μm.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is illustrated by way of example, and not by wayof limitation, in the figures of the accompanying drawings in which likereferences indicate similar elements. It should be noted that differentreferences to “an” or “one” embodiment in this disclosure are notnecessarily to the same embodiment, and such references mean at leastone.

FIG. 1A depicts a sectional view of one embodiment of a processingchamber;

FIG. 1B depicts a sectional view of one embodiment of a showerhead for aprocessing chamber;

FIG. 2 illustrates one embodiment of a bottom view of a showerhead, inaccordance with an embodiment;

FIG. 3A illustrates a method of forming an advanced barrier oxide layeraccording to an embodiment;

FIG. 3B illustrates another method of refurbishing and forming anadvanced barrier oxide layer according to another embodiment;

FIG. 4 illustrates an example architecture of a manufacturing system;

FIG. 5 is a flow chart representing a method of forming an advancedbarrier oxide layer according to an embodiment;

FIG. 6 is a flow chart representing a method of refurbishing and formingan advanced barrier layer according to another embodiment;

DETAILED DESCRIPTION

Embodiments disclosed herein describe coated articles, coated chambercomponents, methods of coating articles and chamber components, methodsof reducing or eliminating particles from semiconductor processingchambers, and methods of using coated articles and chamber componentsand processing chambers containing coated chamber components. To reducereactions between component materials and reactive chemicals and/orplasmas, which form metal fluorides, particles, other trace metalcontaminates and/or high vapor pressure gases, a metal layer (e.g.,which may be a metal coating or metal plating) with a barrier layer isincluded. The metal layer may be a nickel-containing layer (e.g., a purenickel layer or a layer having nickel as a primary constituent andadditionally including other materials such as phosphorous and/orvanadium). The barrier layer may be a nickel oxide layer formed undercontrolled conditions. The barrier layer may be added to new chambercomponents to improve a lifespan of the chamber components and/or toreduce or eliminate a buildup of a contamination layer on the chambercomponent. Further, to improve the life of the coated articles or coatedchamber components (which may be new or used chamber components), theymay be treated to remove a contamination layer and to add a barrierlayer over a metal layer on the chamber components.

It has been found that there is an interaction between fluorine and ametal layer (e.g., an ENP comprising nickel) on chamber components thatadds oxides and/or fluorides to the metal layer. A native oxidenaturally occurs on the metal layer due to exposure to air. However, thenative oxide has undesirable properties. In particular, the native oxideinteracts with process gases (e.g., fluorine) to form a contaminationlayer. The native oxide's interaction with fluorine causes discolorationand forms a black film (contamination layer) over the metal coating thatproduces particles that can contaminate processed substrates. If a blackfilm/contamination layer is present on a chamber component such as ashower head, there may be a drop in yield for substrates processed bythe process chamber that includes the shower head having thecontamination layer.

Further, if there is a black film/contamination layer that forms whilethe chamber component is in use, the chamber component is removed andreplaced.

Thus, embodiments improve the surface of chamber components such asshowerheads to prevent the formation of the black film/contaminationlayer over a metal layer of the chamber components. It would beadvantageous to have a protective barrier layer to prevent the chemicaldegradation of the surface metal layer and formation of the blackfilm/contamination layer. Such a chamber component having a protectivebarrier layer may also degrade and/or become contaminated more slowlythan a chamber component lacking the barrier layer, which may cause thechamber component with the barrier layer over the metal layer to have ahigher mean wafers between cleaning than a chamber component with ametal layer and lacking the barrier layer. The mean wafers betweencleaning represents the mean number of wafers that are processed betweeneach cleaning of the chamber component. Such an increased mean wafersbetween cleaning may be particularly pronounced for chamber componentsused in chambers that perform processes at higher temperatures of about200° C. or above.

In embodiments disclosed herein are chamber components for processingchambers and/or processing chambers containing such chamber components(e.g., semiconductor processing chambers), wherein the chambercomponents include a chamber component and a metal layer (e.g., a metalplating or a metal coating) on at least one surface of the chambercomponent. The metal layer may include an advanced barrier layer inembodiments.

In some embodiments, a chamber component may include a metal layer on asurface of the substrate. The chamber component or portions thereof maybe composed of, without limitation, one or more of a metal, for example,aluminum, stainless steel and/or titanium, a ceramic, for example,alumina, silica and/or aluminum nitride, and/or combinations thereof.The metal layer may be an electroless metal plating including nickel oran electrolytic metal plating including nickel.

In some embodiments, a chamber component may be plated using anelectroless plating process to form an electroless metal plating on oneor more surface of the chamber component. In embodiments, theelectroless metal plating may be a nickel-phosphorous plating. Theelectroless plating process can form a metal plating directly on thesurface of the chamber component. In some embodiments, the chambercomponent may be plated using an electrolytic metal plating process. Forexample, the electrolytic plating process may form a layer containingnickel, silver and/or gold. In some embodiments, one or more surface ofthe chamber component may be coated using a sputtering process, such asa sputtering process that sputters a nickel-containing coating onto theone or more surface of the chamber component. The nickel containingcoating may include, for example, 98-99 atomic % nickel and 1-2 atomic %vanadium.

In some embodiments, when the chamber component is coated with anelectroless plating process, the chamber component is placed in a baththat contains nickel and phosphorous. The bath may include about 84%nickel and about 16% phosphorous, about 86% nickel and 14% phosphorous,about 88% nickel and about 12% phosphorous, about 90% nickel and about10% phosphorous, about 92% nickel and about 8% phosphorous, about 94%nickel and about 6% phosphorous, and about 96% nickel and about 4%phosphorous. For example, the bath may include about 84-96% nickel andabout 4-16% phosphorous.

In some embodiments, when the chamber component is plated with anelectrolytic metal plating process, the coating is free of phosphorous.For example, the plating may be 100% nickel. In some embodiments, thechamber component is coated with a sputtered nickel. The sputterednickel, as understood by one of skill in the art, may include nickel andvanadium. The vanadium may be present in the sputtered nickel in about1% to about 2%.

In embodiments, when the chamber component includes a metal layer thatis an electroless nickel plating or an electrolytic Ni plating, thelayer may be in a thickness from about 20 microns to about 75 microns,from about 25 microns to about 70 microns, from about 30 microns to 60microns, or from about 35 microns to about 50 microns.

In some embodiments, the metal layer may have a hardness from about 450HV to about 500 HV. The roughness of the metal layer may be less than 50μinch in embodiments.

The thickness of the metal layer formed by electroless plating may betargeted based on the amount of time that the chamber component is inthe bath. The chamber component may be in the bath for about one minuteto about three minutes to form the metal layer having a targetthickness.

In some embodiments, a contamination layer may be found on the metallayer. The contamination layer may include a combination of nickel,fluorine and/or oxygen. In embodiments, the metal layer is a nickellayer that becomes slowly fluorinated over time due to exposure tofluorine-rich chemistries. For example, a contamination layer of nickelfluorine and/or nickel oxy-fluorine may be formed on the surface of themetal layer. The contamination layer may react to process gasesdifferently than the metal layer, and may cause subtle changes toprocess chemistries. Additionally, or alternatively, the contaminationlayer may flake off of the chamber component and/or cause particlecontamination on substrates processed in the process chamber in whichthe chamber component is installed. As a result, periodic maintenancemay be performed on chamber components to remove those chambercomponents that include the contamination layer and to replace theremoved chamber components with new chamber components that lack thecontamination layer.

In embodiments, the chamber component includes a barrier layercomprising nickel oxide over a metal layer (e.g., a nickel layer). Inembodiments, the formation of the barrier layer (e.g., the nickel oxidebarrier layer) on the metal layer protects the metal layer from attackby process gases, and in particular to attack by fluorine-containingplasmas and other fluorine-containing chemistries. Accordingly, thebarrier layer may be referred to as a protective layer. The nickel oxidebarrier layer may be formed using an oxidation process, which mayinclude immersing the chamber component (or a portion thereof that is tohave a nickel oxide barrier layer) into a bath containing an oxidationagent (e.g., a bath containing hydrofluoric acid and/or nitric acid withwater).

In some embodiments, the chamber component includes generating a nickelfluorination (NiF₂) or nickel oxy-fluorination (NiOF) layer afterremoving the contamination layer and before forming the barrier layer.The nickel fluorination or nickel oxy-fluorination layer may begenerated by placing the metal plated chamber component in a bath withan ammonium fluoride (NH₄F) solution. The ammonium fluoride solution mayhave a concertation from about 0.5 M to about 3 M. The metal platedchamber component remains in the bath for about 5 minutes to about 60minutes at a temperature of about 35 to about 45° C. to form a nickelfluorinated or nickel oxy-fluorinated layer. If a nickel fluorinatedlayer is formed, then Ni is present in an amount of abut 60 wt. % and Fis present in an amount of about 40 wt. %. If a nickel oxy-fluorinatedlayer is formed, then Ni is present in an amount of about 62 wt. %, F ispresent in an amount of about 20 wt %, and O is present in an amount ofabout 17 wt. %. After this nickel fluorination (NiF₂) or nickeloxy-fluorination (NiOF) layer is formed then the nickel oxide barrierlayer may be formed using an oxidation process as described herein.

Experimentation has shown that use of the nickel oxide barrier layerover a nickel layer on chamber components increases the serviceablelifetime of the chamber components by ten times. Accordingly,preventative maintenances may be reduced by two times up to ten times inembodiments as compared to the number and/or frequency of preventativemaintenances performed to service and/or replace chamber componentshaving an exposed nickel layer.

Some embodiments are descried herein with reference to a showerhead, andare particularly useful for coating chamber components having both highaspect ratio features and regions that are directly exposed tobombardment by a plasma. However, the barrier layer described herein canalso be beneficially used on many other chamber components having metallayers that are exposed to plasma, such as chamber components for aplasma etcher (also known as a plasma etch reactor) or other processingchambers including walls, liners, bases, rings, view ports, lids,nozzles, substrate holding frames, electrostatic chucks (ESCs), faceplates, selectivity modulation devices (SMDs), plasma sources,pedestals, and so forth.

Moreover, embodiments are described herein with reference to plated orcoated chamber components and other articles that may cause reducedparticle contamination when used in a process chamber for plasma richprocesses. However, it should be understood that the plated or coatedarticles discussed herein may also provide reduced particlecontamination when used in process chambers for other processes such asnon-plasma etchers, non-plasma cleaners, chemical vapor deposition (CVD)chambers, physical vapor deposition (PVD) chambers, and so forth.

Referring now to the figures, FIG. 1A is a sectional view of aprocessing chamber 100 (e.g., a semiconductor processing chamber) havingone or more chamber components that include a metal layer and a nickeloxide-containing barrier layer over the metal layer in accordance withembodiments of the present disclosure. The processing chamber 100 may beused for processes in which a corrosive plasma environment and/orcorrosive chemistry is provided. For example, the processing chamber 100may be a chamber for a plasma etch reactor (also known as a plasmaetcher), a plasma cleaner, an atomic layer deposition (ALD) chamber thatperforms plasma-enhanced ALD, other deposition chambers, and so forth.Examples of chamber components that may include a metal layer and abarrier layer over the metal layer are a substrate support assembly 148,an electrostatic chuck (ESC), a ring (e.g., a process kit ring or singlering), a chamber wall, a base, a showerhead 130, a gas distributionplate, a liner, a liner kit, a shield, a plasma screen, a flowequalizer, a cooling base, a chamber viewport, a chamber lid, a nozzle,process kit rings, and so on.

In one embodiment, the metal layer is a nickel-containing layer (e.g.,100% nickel or nickel in combination with one or more additionalmaterials such as phosphorous and/or vanadium). In one embodiment, thebarrier layer is a nickel-oxide containing layer (e.g., 100% nickeloxide or nickel oxide with one or more additional materials such asphosphorous and/or vanadium). The metal layer and the barrier layer maybe conformal thin films.

In one embodiment, the processing chamber 100 includes a chamber body102 and a showerhead 130 that enclose an interior volume 106. Theshowerhead 130 may or may not include a gas distribution plate. Forexample, the showerhead may be a multi-piece showerhead that includes ashowerhead base and a showerhead gas distribution plate bonded to theshowerhead base. Alternatively, the showerhead 130 may be replaced by alid and a nozzle in some embodiments, or by multiple pie shapedshowerhead compartments and plasma generation units in otherembodiments. The chamber body 102 may be fabricated from aluminum,stainless steel or other suitable material. The chamber body 102generally includes sidewalls 108 and a bottom 110. Any of the showerhead130 (or lid and/or nozzle), sidewalls 108 and/or bottom 110 may includethe multi-layer plasma resistant coating.

An outer liner 116 may be disposed adjacent the sidewalls 108 to protectthe chamber body 102. The outer liner 116 may be a halogen-containinggas resist material such as Al₂O₃ or Y₂O₃. The outer liner 116 may becoated with the multi-layer plasma resistant ceramic coating in someembodiments.

An exhaust port 126 may be defined in the chamber body 102, and maycouple the interior volume 106 to a pump system 128. The pump system 128may include one or more pumps and throttle valves utilized to evacuateand regulate the pressure of the interior volume 106 of the processingchamber 100.

The showerhead 130 may be supported on the sidewalls 108 of the chamberbody 102 and/or on a top portion of the chamber body. The showerhead 130(or lid) may be opened to allow access to the interior volume 106 of theprocessing chamber 100, and may provide a seal for the processingchamber 100 while closed. A gas panel 158 may be coupled to theprocessing chamber 100 to provide process and/or cleaning gases to theinterior volume 106 through the showerhead 130 or lid and nozzle. Theshowerhead 130 includes multiple gas delivery holes 132 throughout theshowerhead 130. The showerhead 130 may be or include aluminum, anodizedaluminum, an aluminum alloy (e.g., Al 6061), or an anodized aluminumalloy. In some embodiments, the showerhead includes a gas distributionplate (GDP) bonded to the showerhead. The GDP may be, for example, Si orSiC. The GDP may additionally include multiple holes that line up withthe holes in the showerhead.

FIG. 1B illustrates a zoomed in view of a portion of the showerhead 130of FIG. 1A. With reference to FIG. 1B, in embodiments the showerhead 130is coated by a metal layer 150 and a barrier layer 152. In particular,in some embodiments a surface of the showerhead and walls of holes 132in the showerhead are coated by a thin conformal metal layer 150.Additionally, the backside of the showerhead 130 and outer side walls ofthe showerhead may also be coated by the conformal metal layer 150. Anon-line of sight deposition technique such as ALD or plating (e.g.,electroplating or electroless plating) may be used to deposit or formthe metal layer 150 on the surface of the showerhead 130 and on thewalls of the holes 132 in the showerhead 130. Alternatively, aline-of-sight deposition technique such as sputtering may be used toform the metal layer. The metal layer 150 may be nickel, nickel dopedwith phosphorous, or nickel doped with vanadium in embodiments.

A barrier layer 152 covers the metal layer 150 at some or all regions ofthe surface of the showerhead 130. The barrier layer 152 may be formedusing an oxidation process, which may be a dry oxidation process or awet oxidation process (e.g., by dipping the showerhead 130 into a bathcontaining an oxidizing agent such as hydrofluoric acid or nitric acid.The barrier layer 152 may cover the metal layer on all surfaces of thechamber component, including on the inner walls of holes in theshowerhead 130. The barrier layer may be a grown layer and may beconformal and uniform in embodiments. The uniform barrier layer may havea difference in thickness of less than about 10% across the surface ofthe showerhead in embodiments.

Examples of processing gases that may be used to process substrates inthe processing chamber 100 include halogen-containing gases, such asC₂F₆, SF₆, SiCl₄, HBr, NF₃, CF₄, CHF₃, CH₂F₃, F, Cl₂, CCl₄, BCl₃ andSiF₄, among others, and other gases such as O₂, or N₂O. Examples ofcarrier gases include N₂, He, Ar, and other gases inert to process gases(e.g., non-reactive gases). The fluorine based gases may cause fluoridedeposits to buildup on the holes of standard showerheads and/or acontamination layer to form on the holes of the showerheads. However,the holes 132 of showerhead 130 may be resistant to such fluoridebuildup due to the barrier layer 152.

Referring back to FIG. 1A, a substrate support assembly 148 is disposedin the interior volume 106 of the processing chamber 100 below theshowerhead 130. The substrate support assembly 148 holds a substrate 144(e.g., a wafer) during processing. The substrate support assembly 148may include an electrostatic chuck that secures the substrate 144 duringprocessing, a metal cooling plate bonded to the electrostatic chuck,and/or one or more additional components. An inner liner may cover aperiphery of the substrate support assembly 148. The inner liner may bea halogen-containing gas resist material such as Al₂O₃ or Y₂O₃. Thesubstrate support assembly, portions of the substrate support assembly,and/or the inner liner may be coated with the metal layer and barrierlayer in some embodiments.

FIG. 2 illustrates one embodiment of a bottom view of a showerhead 200.The showerhead 200 may have a series of gas conduits 204 (also referredto as holes) arranged concentrically that evenly distribute plasmagasses directly over a substrate or wafer to be etched or processed. Theshowerhead is depicted here having approximately 1100 gas conduits 204arranged in evenly distributed concentric rings for even distributing ofgasses. In another embodiment, the gas conduits 204 may be configured inalternative geometric configurations on the lower surface 205 of theshowerhead (or on a lower surface of a GDP bonded to a showerhead). Forexample, the showerhead may have a square or rectangular configurationhaving rows and columns of gas conduits 204. It is to be understood thatother shapes (e.g., triangle, pentagon, etc.) may be implemented andcoated with a ceramic coating (e.g., an HPM coating) as described above.The showerhead 200 can have many gas conduits 204, as depicted, or asfew gas conduits as appropriate depending on the type of reactor and/orprocess utilized.

In one embodiment, some or all gas conduits 204 do not include branches(e.g., each gas conduit may have a single entry point and a single exitpoint). Additionally, the gas conduits may have various lengths andorientation angles. Gas may be delivered to the gas conduits 204 via oneor more gas delivery nozzles. Some gas conduits 204 may receive the gasbefore other gas conduits 204 (e.g., due to a proximity to a gasdelivery nozzle). However, the gas conduits 204 may be configured todeliver gas to a substrate resting beneath the showerhead atapproximately the same time based on varying the orientation angles,diameters and/or lengths of the gas conduits 204, or by using anadditional flow equalizer. For example, gas conduits 204 that willreceive gas first may be longer and/or have a greater angle (e.g., anangle that is further from 90 degrees) than conduits that will receivegas later.

As can be seen in FIG. 3A, a schematic 300 of oxidizing the metal platedcoated chamber component is illustrated. In FIG. 3A, a metal platedchamber component includes a nickel layer 301 and a bare aluminum body302 of the chamber component, wherein the nickel layer 301 is on asurface of the bare aluminum body 302. The metal plated chambercomponent undergoes an oxidation process 305 according to the presentdisclosure. After being oxidized, the metal plated chamber componentincludes a dense barrier layer 303 of nickel oxide on a surface of thenickel layer 301. The barrier layer 303 of NiO may prevent discolorationof the metal layer. The barrier layer 303 may also prevent as thechamber component from becoming a source of particles on processedsubstrates. The barrier layer 303 of NiO may also inhibit the reactionof fluorine with nickel in the nickel layer 301 to prevent the formationof a discolored/contaminated layer.

Further, the barrier layer 303 may prevent a native oxide from formingon the nickel layer 1.

In some embodiments, the chamber component may be a used chambercomponent that has been used to perform one or more processes onsubstrates, where the processes exposed the substrates to afluorine-rich environment. The chamber component may not have beencoated with a barrier layer prior to use. Accordingly, the chambercomponent may include a contamination layer over the metal layer 302. Insome embodiments, the chamber component may be refurbished by removingthe contamination layer to expose the metal layer, and then form thebarrier layer over the metal layer. A schematic of such embodiment isillustrated in schematic 350 of FIG. 3B.

In FIG. 3B, the chamber component includes an aluminum body 302 having ametal layer 301 disposed thereon, and a contamination layer 310 over themetal layer 301. The chamber component may undergo a cleaning process315 to strip the contamination layer 310 from the metal layer 301. Thechamber component having the cleaned metal layer 301 may then beprocessed using an oxidation process 305 to form barrier layer 303, asdescribed in more detail in the present disclosure. After cleaning andoxidization, the contamination layer 310 is removed and a barrier layer303 of dense nickel oxide is present over the metal layer 301.

FIG. 4 illustrates an example architecture of a manufacturing system400. The manufacturing system 400 may be a manufacturing system forapplying platings and/or coatings to articles such as chambercomponents. In one embodiment, the manufacturing system 400 includesmanufacturing machines 401 (e.g., processing equipment) connected to anequipment automation layer 415. The manufacturing machines may include apolisher 402, one or more wet cleaners 403, a plating system 404, asputtering system 405, an oxidation system 406, and/or other machines.The manufacturing system 400 may further include one or more computingdevice 420 connected to the equipment automation layer 415. Inalternative embodiments, the manufacturing system 400 may include moreor fewer components. For example, the manufacturing system 400 mayinclude manually operated (e.g., off-line) manufacturing machines 401without the equipment automation layer 415 or the computing device 420.

Polisher 402 is a machine configured to polish or smoothen the surfaceof articles such as chamber components for processing chambers. Polisher402 may be, for example, a chemical mechanical planarization (CMP)device or an abrasive polisher. For example, a motorized abrasive padmay be used to smoothen the surface of an article. A sander may rotateor vibrate the abrasive pad while the abrasive pad is pressed against asurface of the article. A roughness achieved by the abrasive pad maydepend on an applied pressure, on a vibration or rotation rate and/or ona roughness of the abrasive pad.

Wet cleaners 403 are cleaning apparatuses that clean articles (e.g.,articles) using a wet clean process. Wet cleaners 403 include wet bathsfilled with liquids, in which the substrate is immersed to clean thesubstrate. Wet cleaners 403 may agitate the wet bath using ultrasonicwaves during cleaning to improve a cleaning efficacy. This is referredto herein as sonicating the wet bath.

In some embodiments, wet cleaners 403 include a first wet cleaner thatcontains deionized (DI) water and a second wet cleaner that contains anacid solution. The acid solution may be a hydrofluoric acid (HF)solution, a hydrochloric acid (HCl) solution, a nitric acid (HNO₃)solution, or combination thereof in embodiments. The acid solution mayremove surface contaminants from the article and/or may remove an oxidefrom the surface of the article. Cleaning the article having a metallayer with the acid solution prior to forming a barrier layer over themetal layer may improve a quality of the barrier layer formed over themetal layer. In one embodiment, an acid solution containingapproximately 5 to 15 vol % HF is used to clean chamber componentshaving a nickel layer. In one embodiment, an acid solution containingapproximately 5 to 15 vol % HNO₃ is used to clean articles having anickel layer.

The wet cleaners 403 may clean articles at multiple stages duringprocessing. For example, wet cleaners 403 may clean an article after asubstrate has been polished, before performing plating (e.g.,electroplating), before forming a barrier layer over a metal plating,and so on.

In other embodiments, alternative types of cleaners such as dry cleanersmay be used to clean the articles. Dry cleaners may clean articles byapplying heat, by applying gas, by applying plasma, and so forth.

Plating system 404 is a system that performs electroplating (e.g., ofNi) or electroless plating (e.g., of Ni). Plating system 404 may be anelectroplating system that applies a current to reduce dissolved metalcations so that they form a thin coherent metal coating on the article(e.g., on surfaces of a chamber component such as an aluminum chambercomponent). Specifically, the article to be plated may be the cathode ofa circuit and a metal donor may be the anode of the circuit. The articleand metal donor may be immersed in an electrolyte containing one or moredissolved metal salts and/or other ions that increase an electricalconductivity of the electrolyte. Metal from the metal donor than platesa surface of the article.

Another type of plating system that may be used is an electrolessplating system that performs electroless plating. Electroless plating,also known as chemical or auto-catalytic plating, is a non-galvanicplating method that involves several simultaneous reactions in anaqueous solution, which occur without the use of external electricalpower. The reaction is accomplished when hydrogen is released by areducing agent, normally sodium hypophosphite or thiourea, and oxidized,thus producing a negative charge on the surface of the part.

The equipment automation layer 415 may interconnect some or all of themanufacturing machines 401 with computing devices 420, with othermanufacturing machines, with metrology tools and/or other devices. Theequipment automation layer 415 may include a network (e.g., a locationarea network (LAN)), routers, gateways, servers, data stores, and so on.Manufacturing machines 401 may connect to the equipment automation layer415 via a SEMI Equipment Communications Standard/Generic Equipment Model(SECS/GEM) interface, via an Ethernet interface, and/or via otherinterfaces. In one embodiment, the equipment automation layer 415enables process data (e.g., data collected by manufacturing machines 401during a process run) to be stored in a data store (not shown). In analternative embodiment, the computing device 420 connects directly toone or more of the manufacturing machines 401.

In one embodiment, some or all manufacturing machines 401 include aprogrammable controller that can load, store and execute processrecipes. The programmable controller may control temperature settings,gas and/or vacuum settings, time settings, etc. of manufacturingmachines 401. The programmable controller may include a main memory(e.g., read-only memory (ROM), flash memory, dynamic random accessmemory (DRAM), static random access memory (SRAM), etc.), and/or asecondary memory (e.g., a data storage device such as a disk drive). Themain memory and/or secondary memory may store instructions forperforming heat treatment processes described herein.

The programmable controller may also include a processing device coupledto the main memory and/or secondary memory (e.g., via a bus) to executethe instructions. The processing device may be a general-purposeprocessing device such as a microprocessor, central processing unit, orthe like. The processing device may also be a special-purpose processingdevice such as an application specific integrated circuit (ASIC), afield programmable gate array (FPGA), a digital signal processor (DSP),network processor, or the like. In one embodiment, programmablecontroller is a programmable logic controller (PLC).

In one embodiment, the manufacturing machines 401 are programmed toexecute recipes that will cause the manufacturing machines to polish anarticle, clean an article, plate an article, form a barrier layer on anarticle, and so on. In one embodiment, the manufacturing machines 401are programmed to execute recipes that perform operations of amulti-step process for manufacturing an article having a metal layer anda barrier layer, as described with reference to FIGS. 5-6 . Thecomputing device 420 may store one or more plating, oxidizing, cleaningand/or polishing recipes 425 that can be downloaded to the manufacturingmachines 401 to cause the manufacturing machines 401 to manufacturearticles in accordance with embodiments of the present disclosure.

FIG. 5 is a flow chart representing a method 500 of refurbishing, andforming an advanced barrier oxide layer on, a chamber componentaccording to an embodiment. Method 500 may be performed on chambercomponents having a metal layer (e.g., a metal plating) that has beenused to perform one or more cycles of one or more manufacturingprocesses that expose the chamber component to chemistries that causeformation of a contamination layer on the metal layer. The contaminationlayer may contain oxygen, fluorine and/or one or more process elements.The contamination layer may cause particle contamination and/ornegatively affect future processes performed in the process chamber inembodiments. Accordingly, in some embodiments of the present disclosure,when a contamination layer is present on the metal plated chambercomponent, the chamber component is placed in a first bath 502. Thefirst bath may include water and a first acid (e.g., hydrofluoric acid,nitric acid (HNO₃), sulfuric acid (H₂SO₄), oxalic acid (HC₂O₄), orammonium fluoride (NH₄F)). The hydrofluoric acid may be included in anamount from about 5 wt. % to about 15 wt. % in the bath based on thetotal composition of the first bath. The water may be included in anamount from about 85 wt. % to about 95 wt. % in the bath based on thetotal composition of the bath. In some embodiments, the first bathincludes about 5 wt. % hydrofluoric acid and about 95 wt. % water. Thefirst bath may be at a temperature from about 25° C. to about 35° C. Theused metal plated chamber component may be placed in the first bath forabout one minute to about 30 minutes to loosen the contamination layer.After soaking in the first bath, the metal plated chamber may include aloosened contamination layer. The metal plated chamber component maythen be rinsed (e.g., with deionized water) to remove the loosenedcontamination layer and dried at block 504.

Subsequently, the metal plated chamber component is placed into thefirst bath or a second bath at block 506. The second bath includes waterand an acid (e.g., hydrofluoric acid). The acid may be included in anamount from about 5 wt. % to about 15 wt. % in the bath based on thetotal composition of the first bath or second bath. The water may beincluded in an amount from about 85 wt. % to about 95 wt. % in the bathbased on the total composition of the first bath or second bath. In someembodiments, the second bath includes about 5 wt. % hydrofluoric acidand about 95% water. The second bath may be at a temperature from about25° C. to about 35° C. The used metal plated chamber component may beplaced in the second bath for about one minute to about 30 minutes,where the remaining contamination layer may be removed. After the secondbath, the metal plated chamber component may be rinsed (e.g., withdeionized water) and dried 508.

The metal plated chamber component may then be polished after removingthe contamination layer 510. The metal plated chamber component may bepolished using an automatic polisher with different polishing sheets,such as a Scotch-Brite® sheet, or another advanced method to uniformlypolish a surface. The metal plated coated chamber component may bepolished until the surface roughness is about 10 μin to about 20 μin inone embodiment. After polishing, the metal plated coated chambercomponent may undergo an oxidation treatment 512. The oxidationtreatment may be performed by placing the metal plated coated chambercomponent in a third bath. The third bath includes water and an acid(e.g., nitric acid (HNO₃), sulfuric acid (H₂SO₄), oxalic acid (HC₂O₄),or ammonium fluoride (NH₄F)). The acid may be included in an amount fromabout 5 wt. % to about 25 wt. % in the bath based on the totalcomposition of the third bath. The water may be included in an amountform about 75 wt. % to about 95 wt. % in the bath based on the totalcomposition of the third bath. In some embodiments, the third bath mayinclude about 5 wt. % hydrofluoric acid and about 95 wt. % water. Thethird bath may be at a temperature from about 25° C. to about 35° C. Themetal plated chamber component may be placed in the third bath for aboutone minute to about 30 minutes. The oxidized metal plated chambercomponent may be rinsed (e.g., with deionized water), where a nickeloxide layer may be formed on the surface of the metal plating layer. Thenickel oxide layer may be between about 5 nanometers to about 35nanometers in one embodiment.

In another embodiment, the metal plated coated chamber component may bea new component, which may be oxidized through a second method 600. FIG.6 is a flow chart representing a method of forming an advanced barrierlayer on a metal plated or metal coated chamber component according toan embodiment. In the second method 600, the metal plated chambercomponent is placed in a first bath 602. The first bath may includewater and an acid (e.g., hydrofluoric acid). The hydrofluoric acid maybe included in an amount from about 5 wt. % to about 25 wt. % in thebath based on the total composition of the first bath. The water may beincluded in an amount form about 75 wt. % to about 95 wt. % in the bathbased on the total composition of the bath. In some embodiments, thefirst bath includes about 5 wt. % hydrofluoric acid and about 95 wt. %water. The first bath may be at a temperature from about 25° C. to about35° C. The metal plated chamber component may be placed in the firstbath for about one minute to about 30 minutes. After the first bath 604,the metal plated chamber component may be rinsed (e.g., with deionizedwater) and dried 606.

Once dried, the metal plated chamber component may be treated with anacid (e.g., hydrofluoric acid or nitric acid (HNO₃)) to oxidize themetal plating layer and form a nickel oxide layer 608. The metal platedcoated chamber component may be treated for a time from about one minuteto about 30 minutes until a target thickness of the nickel oxide layeris achieved. The nickel oxide layer may be between about 5 nanometers toabout 30 nanometers in embodiments, such as about 15 nanometers. Themetal plated coated chamber component is then rinsed with deionizedwater and dried at block 610.

In another embodiment, the metal plated coated chamber component may bea new component, having a nickel fluorinated or nickel oxy-fluorinatedlayer, and oxidizing the chamber component. FIG. 7 is a flow chartrepresenting a method of forming an advanced barrier layer on a metalplated or metal coated chamber component having a nickel fluorinated(NiF₂) or nickel oxy-fluorinated (NiOF) layer according to anembodiment. The chamber component is placed in a first bath and rinsedin steps 702 to 706, as described in FIG. 6 , steps 602 to 606. Afterrinsing and drying the chamber component, the chamber component is thenplaced in a second bath including an ammonium fluoride solution 708 toform a nickel fluorine or nickel oxy-fluorine layer. The ammoniumfluoride solution has a concentration of about 0.5M to about 3 M. Thechamber component remains in the second bath for about 5 minutes toabout 60 minutes, where the second bath is at a temperature of about 35to 45° C. to form a NiF₂ or NiOF layer. The chamber component is thenremoved from the bath 710. The chamber component is then rinsed anddried in step 712 as described above for step 606 in FIG. 6 . Afterformation of the NiF₂ or NiOF layer, the chamber component may betreated with an acid (e.g., hydrofluoric acid or nitric acid (HNO₃)) tooxidize the metal plating layer 718 and form a nickel oxide layer asdescribed above in steps 512 and 608 in FIGS. 5 and 6 , respectively.

In another embodiment, the metal plated chamber component may beoxidized through an in situ method. This method may occur in the samechamber in which the chamber component is being coated with the nickelplated coating or in the chamber in which the part will be used. In afirst step of the in situ method, the metal plated chamber component maybe treated with a gas and moisture while the chamber component is in thechamber. The gas may be selected from the group consisting of NH₃, NF₃,HF or H₂, or a combination thereof. In some embodiments, the gas may bea combination of NH₃ and NF₃ or NH₃, NF₃ and HF. The gas may be in aconcentration from about 5 sccm to about 2000 sccm of total gas. The gasreacts with the ambient moisture within the chamber. The temperature ofthe chamber be from about 150° C. to about 220° C. The nickel oxidecoating layer may have a thickness of about 4 nm to about 50 nm.

By treating the part with an oxidation treatment to form a barrier layeras described herein, the inventors have found that the lifetime of thepart may be more than 10 times that of the original coating that lacksthe barrier layer. When an ENP coated layer chamber component is used,the standard lifetime is about 3000 cycles. When a barrier nickel oxidelayer is present on the ENP coated layer, the lifetime of the partincreases almost 10 times more than the standard lifetime of the part,where the lifetime is greater than 10,000 cycles.

Further, the inventors have found that the oxidation method can be usedto coat a new part and for refurbishing an existing part where acontamination layer has formed.

ILLUSTRATIVE EXAMPLES

The following examples are set forth to assist in understanding thedisclosure and should not be construed as specifically limiting thedisclosure described and claimed herein. Such variations of thedisclosure, including the substitution of all equivalents now known orlater developed, which would be within the purview of those skilled inthe art, and changes in formulation or minor changes in experimentaldesign, are to be considered to fall within the scope of the disclosureincorporated herein.

Example 1—Pretreatment of an ENP Coated Showerhead

Exemplified herein is a showerhead having a nickel plating and a nickeloxide barrier layer on the nickel plating. The showerhead was firstcoated with nickel layer using a metal plating process. A natural oxidelayer was formed on the nickel plating prior to formation of anintentional nickel oxide layer. The natural nickel oxide layer hasinferior properties and impedes the formation of a target nickel oxidelayer that will reduce particle contamination and improve a lifespan ofthe chamber component. The native nickel oxide layer may have athickness of about 2 to 3 nm. The showerhead then underwent anoxidization treatment in which the showerhead was placed in a bath of 5%(5%-25%) hydrofluoric acid and 95% water at a temperature between 25 to35° C. After 40 minutes, the showerhead was removed from the bath andrinsed with deionized water. A barrier nickel oxide layer was formedover the nickel layer. The barrier nickel oxide (NiO) layer on the metallayer had a thickness of from about 6 nm to about 22 nm.

Example 2—Cleaning and Oxidizing of an ENP Coated Showerhead

Exemplified herein is a showerhead comprising a nickel plating (a nickelENP) that has been used, where a contamination layer has formed on theshowerhead as a result of the use. The total thickness of thecontamination layer (i.e., a fluorinated or oxy-fluorinated layer) wasgreater than 5 to 200 nm.

The showerhead was cleaned to remove the contamination layer by placingthe showerhead in a first bath of 5% (5%-25%) hydrofluoric acid and 95%water for 40 minutes at 25 to 40° C. The showerhead was then removedfrom the first bath and rinsed with deionized water and dried. After itwas dried, the showerhead was then placed in a second bath of 25%hydrofluoric acid and 75% water for 40 minutes at 25 to 40° C. Theshowerhead was then removed from the second bath and rinsed again withdeionized water and dried.

The contamination layer was removed from the showerhead as a result ofthe cleaning. The showerhead was then treated and oxidized by placingthe showerhead in a bath of 5% hydrofluoric acid to form a barrier layerover the ENP layer. A barrier nickel oxide layer was formed on the ENPlayer as a result of the treatment and oxidation. The barrier nickeloxide (NiO) layer on the ENP coating layer had a combined thickness ofabout 22 nm. An EDS line profile of the barrier NiO layer on the ENPlayer showed that nickel was present in the barrier NiO layer and therewas no phosphorous in such layer. A TEM image and an EDS line profile ofan inside of a small hole of the showerhead was also taken, and showedthat the barrier layer had a thickness between 6.3 nm to 31.2 nm.

The barrier layer on the backside of the showerhead was also measured tohave a thickness of about 19 to 30 nm. This was also shown in an EDSline profile. This confirms that the barrier nickel oxide layer wasformed along the entire showerhead, and was not limited to only thefront side of the showerhead.

Example 3—Fluorination and Oxidizing of an ENP Coated Showerhead

Exemplified herein is a showerhead comprising a nickel plating (a nickelENP) coating that is treated with ammonium fluoride (NH₄F) solutionhaving a concentration of 0.5M to 3M to convert a fluorinated (NiF₂) oroxidized-fluorinated (NiOF) layer having a thickness of about 6 nm toabout 50 nm. The showerhead underwent an oxidization treatment in whichthe showerhead was placed in a bath of 5% (5%-25%) hydrofluoric acid and95% water at a temperature between 25 to 35° C. to have a NiO thicknessof about 6 nm to about 50 nm.

SEM images were also taken of the barrier layer on the ENP coatedshowerhead. From the SEM images, the weight percent of C, O, P and Niwere calculated and are presented in Table 1. It is noted that P comesfrom the ENP layer.

TABLE 1 Element Weight % Atomic % C K 12.62 35.92 O K 4.08 8.72 P K13.16 14.52 Ni K 70.14 40.84 Totals 100.00

The preceding description sets forth numerous specific details such asexamples of specific systems, components, methods, and so forth, inorder to provide a good understanding of several embodiments of thepresent invention. It will be apparent to one skilled in the art,however, that at least some embodiments of the present invention may bepracticed without these specific details. In other instances, well-knowncomponents or methods are not described in detail or are presented insimple block diagram format in order to avoid unnecessarily obscuringthe present invention. Thus, the specific details set forth are merelyexemplary. Particular implementations may vary from these exemplarydetails and still be contemplated to be within the scope of the presentinvention.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure, orcharacteristic described in connection with the embodiment is includedin at least one embodiment. Thus, the appearances of the phrase “in oneembodiment” or “in an embodiment” in various places throughout thisspecification are not necessarily all referring to the same embodiment.In addition, the term “or” is intended to mean an inclusive “or” ratherthan an exclusive “or.” When the term “about” or “approximately” is usedherein, this is intended to mean that the nominal value presented isprecise within ±10%.

Although the operations of the methods herein are shown and described ina particular order, the order of the operations of each method may bealtered so that certain operations may be performed in an inverse orderor so that certain operation may be performed, at least in part,concurrently with other operations. In another embodiment, instructionsor sub-operations of distinct operations may be in an intermittentand/or alternating manner.

It is to be understood that the above description is intended to beillustrative, and not restrictive. Many other embodiments will beapparent to those of skill in the art upon reading and understanding theabove description. The scope of the invention should, therefore, bedetermined with reference to the appended claims, along with the fullscope of equivalents to which such claims are entitled.

1. A chamber component for a processing chamber, comprising: a body, wherein the body comprises aluminum, an aluminum alloy, aluminum nitride, alumina or combinations thereof; a metal plating on at least one surface of the body, the metal plating comprising nickel; and a barrier layer on the metal plating, wherein the barrier layer comprises a nickel oxide and has a thickness of about 5 nanometers to about 35 nanometers.
 2. The chamber component of claim 1, wherein the metal plating comprises nickel and phosphorus.
 3. The chamber component of claim 1, wherein the metal plating comprises nickel and is free of phosphorous.
 4. (canceled)
 5. The chamber component of claim 1, wherein the metal plating has a thickness of about 20 microns to about 75 microns, and wherein the barrier layer has a thickness of about 2 nm to about 50 nm.
 6. The chamber component of claim 1, wherein the barrier layer has an average surface roughness (Ra) of about 2 micro-inches to about 60 micro-inches.
 7. The chamber component of claim 1, wherein the chamber component comprises a showerhead for a process chamber.
 8. A method of protecting a chamber component, comprising: forming a metal plating on a body of the chamber component, wherein the metal plating comprises nickel, and contacting the metal plating with an oxidizing agent to form a barrier layer on the metal plating, wherein the barrier layer comprises nickel oxide.
 9. The method of claim 8, wherein the oxidizing agent comprises at least one of hydrofluoric acid, oxalic acid, or nitric acid.
 10. The method of claim 8, wherein the barrier layer has a thickness from about 2 μm to about 60 μm.
 11. The method of claim 8, wherein forming the metal plating comprises performing electroless metal plating, and wherein the metal plating further comprises phosphorus.
 12. The method of claim 8, wherein the body comprises an aluminum alloy, aluminum nitride, alumina, or combinations thereof.
 13. The method of claim 8, further comprising: removing a native oxide from the metal plating prior to forming the barrier layer.
 14. The method of claim 8, further comprising after the forming the metal playing, forming a nickel fluoride (NiF2) or nickel oxy-fluoride layer on the metal plating by contacting the metal plating with ammonium fluoride.
 15. The method of claim 8, further comprising: placing the chamber component in an acid bath comprising 5-25% hydrofluoric acid and 75-95% water to contact the metal plating with the oxidizing agent; subsequently placing the chamber component in a de-ionized water bath; subsequently placing the chamber component in the acid bath; and subsequently placing the chamber in the di-ionized water bath.
 16. A method of refurbishing a used chamber component, comprising: removing a contamination layer from a metal plating on the used chamber component using a first acid solution, wherein the metal plating comprises nickel; and subsequently contacting the metal plating with an oxidizing agent to form a barrier layer on the metal plating, wherein the barrier layer comprises nickel oxide.
 17. The method of claim 16, wherein the contamination layer comprises nickel fluoride.
 18. The method of claim 16, wherein the removing the contamination layer comprises: placing the used chamber component in a first acid bath, subsequently rinsing the used chamber component with deionized water, subsequently drying the used chamber component, subsequently placing the used chamber component in a second acid bath, subsequently rinsing the used chamber component with deionized water, and subsequently drying the used chamber component.
 19. The method of claim 16, wherein the oxidizing agent comprises at least one of hydrofluoric acid or nitric acid.
 20. The method of claim 16, wherein the barrier layer has a thickness from about 2 μm to about 60 μm. 